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Atmospheric Environment 47 (2012) 51e57

Contents lists available at SciVerse ScienceDirect

Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Impact of Santiago de Chile urban atmospheric pollution on anthropogenic trace

elements enrichment in snow precipitation at Cerro Colorado, Central Andes
F. Cereceda-Balic a, M.R. Palomo-Marn b, E. Bernalte b, V. Vidal a, J. Christie a, X. Fadic a, J.L. Guevara a,1,
C. Miro c, E. Pinilla Gil b, *
a
b
c

Centro de Tecnologas Ambientales, Universidad Tcnica Federico Santa Mara, Av. de Espaa, Valparaso, Chile
Departamento de Qumica Analtica, Facultad de Ciencias, Universidad de Extremadura, Av. de Elvas, s/n. 06006 Badajoz, Spain
Departamento de Fsica Aplicada, Universidad de Extremadura, Campus Universitario, Cceres, Spain

Winter snow precipitation in the Central Andes mountain range reects urban atmospheric emissions of Santiago de Chile by signicant
enrichment of anthropogenic elements. The preliminary results obtained in this study are promising for assignment and tracking of pollution
sources by exploiting chemical information collected in the snow.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 5 July 2011
Received in revised form
2 November 2011
Accepted 16 November 2011

Seasonal snow precipitation in the Andes mountain range is evaluated as an environmental indicator of
the composition of atmospheric emissions in Santiago de Chile metropolitan area, by measuring a set of
representative trace elements in snow samples by ICP-MS. Three late winter sampling campaigns (2003,
2008 and 2009) were conducted in three sampling areas around Cerro Colorado, a Central Andes
mountain range sector NE of Santiago (36 km). Nevados de Chilln, a sector in The Andes located about
500 km south from the metropolitan area, was selected as a reference area. The experimental results at
Cerro Colorado and Nevados de Chilln were compared with previously published data of fresh snow
from remote and urban background sites. High snow concentrations of a range of anthropogenic marker
elements were found at Cerro Colorado, probably derived from Santiago urban aerosol transport and
deposition combined with the effect of mining and smelting activities in the area, whereas Nevados de
Chilln levels roughly correspond to urban background areas. Enhanced concentrations in surface snow
respect to deeper samples are discussed. Signicant differences found between the 2003, 2008 and 2009
anthropogenic source markers proles at Cerro Colorado sampling points were correlated with changes
in emission sources at the city. The preliminary results obtained in this study, the rst of this kind in the
southern hemisphere, show promising use of snow precipitation in the Central Andes as a suitable
matrix for receptor model studies aimed at identifying and quantifying pollution sources in Santiago
de Chile.
2011 Elsevier Ltd. All rights reserved.

Keywords:
Trace elements
Atmospheric pollution
Snow
Santiago de Chile
Central Andes

1. Introduction
Trace elemental proles are key data sets for the assessment of
potential aerosol toxicity and also for pollution sources identication
and quantication (Watson et al., 2002; Viana et al., 2008, and
references therein). Urban aerosol elemental proles are usually
evaluated on aerosol samples obtained at particular city locations or
closely around, but these samples can be potentially affected by
analytical noise due to rapid temporal changes of pollution sources,
and also by the intrinsic heterogeneity of the urban areas. In contrast,
remote sampling may provide clearer information, aside of data
* Corresponding author. Tel.: 34 924 289389; fax: 34 924 274244.
E-mail address: epinilla@unex.es (E. Pinilla Gil).
1
Present address: Departamento de Biologa y Qumica, Facultad de Ciencias
Bsicas, Universidad Catlica del Maule. Avenida San Miguel, 3605. Talca, Chile.
1352-2310/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2011.11.045

about medium and long range transportation of atmospheric aerosol

(Walker et al., 2003; Caritat et al., 2005).
Snow is considered to be an ideal matrix to observe deposition
from the atmosphere. Atmospheric deposition events can be easily
and cheaply sampled in well dened increments. Compared to other
sedimentary records, atmospheric particulates in snow are diluted
by pure water rather than other earth materials so the composition
of atmospheric deposition may be unambiguously measured down
to very low concentrations. Snowakes accumulate more pollutants
from the atmosphere than raindrops because of their larger surface
area and slower fall velocity (Telmer et al., 2004).
A number of studies have dealt with the use of snow as environmental receptor of trace elements, for the identication and
quantication of precipitation sources at remote locations. Local,
regional and long range transports have been identied in the French

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52

F. Cereceda-Balic et al. / Atmospheric Environment 47 (2012) 51e57

Alps (Veysseyre et al., 2001), north eastern European Russia (Walker

et al., 2003), rural locations around a smelter in Quebec (Telmer et al.,
2004), Mt. Everest at Central Himalayas (Kang et al., 2007; Lee et al.,
2008); Italian Dolomites (Gabrielli et al., 2008), or the Pyrenees
(Veschambre, 2006; Bacardit and Camarero, 2010). Less information
is found in the literature about the use of trace elements in snow as
a matrix for the investigation of short range urban pollution.
Anthropogenic enrichment of heavy metals in snow samples around
Lulea, Sweden, has been described (Viklander, 1998, 1999). The same
group has studied the differences among snow samples obtained at
different cities in Sweden (Reinosdotter and Viklander, 2005). Glenn
and Sansalone (2002), measured the Cu, Zn, Pb and Cd levels in snow
samples taken from urban background areas around Cincinnati, OH,
USA. Engelhard et al. (2007) studied the impact of urban pollution on
the composition of seasonal snow at Innsbruck, Austria. No studies
about snow as environmental receptor of trace elements at locations
in the southern hemisphere are reported in the literature.
Santiago de Chile (pop. almost 6 million), is located in a relatively at valley at an altitude of 500 m. The Andes mountain range
is located close to the east, with hills up to 4500 m. A smaller
coastal mountain range is located in the west, with hills up to
2000 m. Due to its subtropical latitude; the vertical exchange of air
during most of the year is controlled by permanent subsidence and
the formation of a thermal inversion layer, caused by the South

Pacic sub-tropical anticyclone (Morata et al., 2008). This results in

a semiarid climate with temperatures ranging between 2 and
35  C (average values around 14  C) and an average rainfall of
350 mm per year with large interannual variability (Ruthlant and
Garreaud, 1995). The thermal inversion subsidence layer lies at
about 400 m above the ground during the winter and the autumn
and at 1000 m during the spring and the summer. During these
thermal inversion periods, the vertical ventilation is highly
restricted and air pollution increases with potential effects on the
nearby mountains. The urban area of Santiago is showing a rapid
growth, concentrating most of the new services, housing and
industries as compared to the rest of the country (Romero et al.,
1999), thus reinforcing the magnitude of this pollution problem.
Intense episodes of air pollution are frequent from April to August
(Ruthlant and Garreaud, 1995), with signicant impact on particulate matter and anthropogenic element contents in the city
(Romo-Krger, 1990; Gramsch et al., 2006; Sax et al., 2007; Morata
et al., 2008). Particle mass concentration (PM10) 24-h averages near
300 mg m3 are frequent in the western part of Santiago (Pudahuel,
Cerrillos). Some isolated events of 500 mg m3 or more occur
several times during winter (Jorquera et al., 1998; Perez et al., 2000;
Artaxo et al., 1999). Some active copper mines and smelters are
present in the proximity of Santiago, including the world class
El Teniente Mine and the associated Caletones smelter. SO2 and

Fig. 1. Map of Central Chile showing the Cerro Colorado (CC) sampling area close to Santiago de Chile and the Nevados de Chilln (NCH) reference sampling area.

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F. Cereceda-Balic et al. / Atmospheric Environment 47 (2012) 51e57

other gaseous pollutants concentrations have increased from 2004

to 2009 due to the operation of additional coal red power plants in
central Chile as a result of the expansion of the copper industry
with a corresponding increase of energy demand.
No reference has been found about the impact of Santiago de
Chile atmospheric emissions on seasonal snow precipitation at the
close Andes heights, so we have conducted a preliminary study to
evaluate this impact by measuring the levels of selected anthropogenic elements in the snow. Aside to the evaluation of potential
usefulness of snow precipitation at Central Andes as a suitable
matrix for receptor model studies (aimed to identify and quantify
pollution sources in Santiago de Chile), this study can also serve as
a starting point to estimate the potential impact of snow pollutants
on receiving water bodies as the winter snow deposits begin to
melt, especially in case of rain-on-snow events, causing rapid
releasing of pollutants from snow piles. This is the rst study of this
type in the southern hemisphere.
2. Materials and methods
2.1. Sampling sites

53

wind. The sampling sites were selected so that they were as far as
possible from local contamination sources such as ski trails, cable
car stations, trees or exposed rocks.
2.3. Analytical procedure
The samples were melted at room temperature under hood
extraction and acidied with subboiled nitric acid to make 5%
solutions. A complete set of trace elements was determined by
ICP-MS using a PerkinElmer ELAN 9000 instrument placed in a clean
room. Analytical determinations were carried out in triplicate on raw
aqueous samples without any preconcentration or pretreatment step
to minimize contamination. Some elements were under the instrument detection limit and other gave no relevant environmental
information, so As, Pb, Cd, Ni, V, Cr, Mn, Co, Ba, Cu, Zn, Mo and Sb
were selected for discussion after screening the data base for relevant results. These elements are classied in the literature as tracers
of diverse anthropogenic activities (Viana et al., 2008 and references
therein). The precision ranged from 10 to 20% depending on the
elements and the concentration levels. Detection limits were calculated according to the IUPAC denition as three times the standard

Snow sampling was conducted in the Cerro Colorado area (33

S, 70 170 W) and in the Nevados de Chilln area (36 540 S, 71
240 W), as depicted in Fig. 1. Cerro Colorado is 36 km NE of Santiago
de Chile downtown, so it is considered to be at a suitable distance
range to test the inuence of the urban atmosphere on the
precipitated snow, especially because of the prevailing SW winds in
the area (Morata et al., 2008). Nevados de Chilln, selected as
a reference area, is a relatively undisturbed sector of The Andes
range, 500 km south of Santiago de Chile. The most signicant
human agglomeration in the area is the city of Chilln (162,000
inhabitants, 60 km NW of the sampling area). Both Cerro Colorado
and Nevados de Chilln are affected by sporting activities based on
nearby skiing facilities and scarce urbanization. The samples were
collected from October 1 to 15 (2003, 2008 and 2009, single
campaigns each year), after the major winter snowfall had occurred
and before the snowpack had started to melt. Three sampling
points were selected at Cerro Colorado, along a transect line from
3000 to 3050 m.a.s.l. (Fig. 2a). Five sampling points were selected at
Nevados de Chilln (Fig. 2b) along the Diguilln Valley from two
altitudes: 1570 (two points) and 1740 (three points) m.a.s.l. Field
duplicates were collected at each sampling point.
200

2.2. Sampling procedure

The purity of snow makes it more prone to contamination and
therefore special handling protocols are required (Veysseyre et al.,
2001). Sampling materials were previously acid cleaned and then
rinsed with ultra pure water obtained by coupling a reverse
osmosis system (Wasserlab, Spain) with a four-column ion
exchange system Milli-Q equipped with a 0.2 mm lter (Millipore,
Bedford, MA). The HNO3 used were subboiled at a quartz distiller
(Krner, Germany). Samples were collected from a 1 square meter
hand-dug shallow snow pit by operators wearing polyethylene
gloves, using acid-cleaned plastic shovels. Approximately 2 kg of
surface snow was then collected from the rst 5 cm of snow, and
then 2 kg of deep snow was collected under 5 cm deep. The
samples were immediately transferred to cleaned polyethylene
bags (Ziploc), sealed and kept frozen at 20  C until analysis.
Appropriate precautions were taken to avoid contamination as
follows: Powderless polyethylene gloves were always used, and the
tools were well cleaned between each use by rinsing with snow
from the subsequent sample site. At each site, sampling was done in
undisturbed snow which was approached by walking into the

Fig. 2. Map showing the location of the sampling sites Cerro Colorado (a) and Nevados
de Chilln (b).

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F. Cereceda-Balic et al. / Atmospheric Environment 47 (2012) 51e57

Table 1
Limits of detection (LOD) calculated from 3s of 10 replicates of blank solution and
analytical results of certied reference material SPS-SW2 Reference material for
measurements of elements in surface waters. All data in mg kg1.
Element

LOD

SPS-SW2 measured

SPS-SW2 certied

As
Pb
Cd
Ni
V
Cr
Mn
Co
Ba
Cu
Zn
Mo
Sb

0.007
0.613
0.013
0.115
0.004
0.025
0.091
0.007
0.714
0.119
0.045
0.025
0.008

5.03  0.83
2.47  0.28
0.25  0.02
4.84  0.30
4.81  0.33
1.02  0.06
4.74  0.53
1.00  0.07
25.06  2.89
10.41  0.75
9.74  1.69
4.92  0.36
1.53  0.51

5.0  0.3
2.5  0.1
0.26  0.02
5.0  0.3
5.0  0.3
1.00  0.05
5.0  0.3
1.00  0.05
25.0  1.0
10.0  1.0
10.0  2.0
5.0  0.3
Not certied

deviation of concentrations estimated after ten repetitive measurement of the blank solution (5% HNO3 in ultrapure water) are reported
in Table 1. The obtained values were low enough for measuring the
expected concentrations in the real samples. A certied reference
material (SPS-SW2 Reference material for measurements of
elements in surface waters, Spectrapure Standards, Oslo, Norway)
was used for quality control of the data. A good agreement between
measured and certied values was observed for most elements
assayed (Table 1). Enrichment of elements in the real snow samples
were calculated as mean element concentration at location 1/mean
element concentration at location 2.
3. Results and discussion
3.1. General overview and comparison with reference areas
Trace element concentrations measured in the surface snow at
the sampling locations Cerro Colorado (CC) and Nevados de Chilln
(NCH) are given in Table 2, aside with literature data about previously reported values of trace elements in fresh snow from locations
that can be considered relatively remote in their regional context
(Pyrenees, Alps, and Alaska). For each area, the quoted values are the
median values and the range (minimum and maximum) of the
whole set of samples obtained during the sampling campaigns. Most
anthropogenic elemental concentrations measured at Cerro
Colorado are higher than corresponding literature values. The

differences were especially signicant in the cases of As, Pb, Cd, Mn,
Co, Ba, Cu, Zn and Mo, whereas Ni and V concentrations were only
slightly higher. Cr and Sb concentrations in Cerro Colorado snow
samples were similar or lower than previously reported values in
regional background areas. These results are in support of a signicant impact of emission sources from Santiago de Chile in the area,
but the data can also reect the impact of miningesmelting activities. The proximity of copper strip mining operations at Los Bronces
(40 km NW of the Cerro Colorado sampling area) is probably related
with the high Cu values observed. The giant El Teniente (mine) e
Caletones (smelter) copper complex (95 km SW), can be also related
with enhanced levels of some elements in the snow of Cerro Colorado as a result of particulate matter transport. Elevated levels of Cu,
Zn and As were measured by Romo-Krger et al. (1994) in particulate
matter around El Teniente e Caletones. Snow samples taken at
Nevados de Chilln presented similar concentration ranges for
anthropogenic elements than literature values for most elements,
except for somewhat elevated values of Pb, Cd, Cu, and Mo. Whereas
Nevados de Chilln has been selected as a regional reference in our
study, the experimental data shown that a signicant degree of
anthropogenic impact is detected in the area. This can be due to
nearby sporting activities, but transport from regional sources can be
implied, including emissions from Chilln (60 km NW) and Concepcin (130 km W). Also, altered composition of particulate matter
in the regional scale, due to geological abnormalities and surface
coverage mobilization by weathering and mining activities is typical
in Chile, and also the regional dispersion of smelting particulate
emissions (Kavouras et al., 2001; De Gregori et al., 2002; Gidhagen
et al., 2002). The regional air dynamics conguration contributes to
this phenomenon, with SW air masses traveling from the coast to the
high slope, west face mountainsides in The Andes.
Anthropogenic elements concentrations at Cerro Colorado and
Nevados de Chilln samples were then compared with previously
reported values for Cu, Zn, Pb and Cd levels in snow sampled from
urban background areas around Cincinnati, OH, USA (Glenn and
Sansalone, 2002), Lulea and Sundsvall in Sweden (Reinosdotter
and Viklander, 2005), and Innsbruck in Austria (Engelhard et al.,
2007). The results are summarized in Table 3. The most notable
feature is probably the very high Cu levels measured at Cerro
Colorado snow samples, with maximum values exceeding one
order of magnitude Nevados de Chilln values and previously
published urban background data. Cu levels at Nevados de Chilln
samples were similar to those reported in the literature. Zn
concentrations in snow samples from Cerro Colorado are in the

Table 2
Element concentration ranges measured values in Cerro Colorado (CC) and Nevados de Chilln (NCH) and comparison with literature values about trace elements in fresh snow
from regional background locations. Concentrations are given in median values and range in brackets. All data in mg kg1.
Element

CC

As
Pb
Cd
Ni
V
Cr
Mn
Co
Ba
Cu
Zn
Mo
Sb

0.55
19.48
0.72
0.70
0.33
0.01
12.25
0.42
5.90
33.29
29.59
0.27
0.03

a
b
c
d
e

NCH
(0.03e3.33)
(2.36e74.86)
(0.13e2.18)
(0.22e4.92)
(0.01e4.94)
(0.01e4.69)
(1.61e133.82)
(0.11e5.34)
(0.64e77.84)
(4.97e386.68)
(10.14e114.46)
(0.06e1.68)
(0.01e0.20)

Veschambre (2006).
Bacardit and Camarero (2010).
Veysseyre et al. (2001).
Gabrielli et al. (2008).
Douglas and Sturm (2004).

0.01 (0.01e0.16)
9.21 (1.85e13.55)
0.18 (0.14e0.83)
0.21 (0.06e0.56)
0.01 (0.01e0.02)
<LOD
0.12 (0.05e2.24)
0.03 (0.02e0.50)
0.42 (0.36e1.75)
3.59 (1.08e17.83)
14.93 (13.20e16.59)
0.01 (0.01e0.39)
0.02 (0.01e0.08)

Atlantic pyreneesa

Central pyreneesb

0.11 (0.07e0.47)
0.05 (0.02e0.07)

0.93 (0.04e9.14)

Chamonix alpsc

Eastern alpsd

0.23 (0.07e1.76)
0.02 (0.008e0.06)

0.87 (0.02e33.70)
0.05 (0.02e0.22)

0.02 (0.004e0.11)

0.13 (0.003e4.6)
0.04 (0.003e3)
1.20 (0.01e173)
0.02 (0.002e0.97)
0.5 (0.009e36.5)
0.28 (0.08e29.1)
1.7 (0.02e63.1)
0.04 (0.01e0.72)
0.03 (0.002e6.2)

0.37 (<LODe1.35)
0.04 (0.02e0.09)
0.04 (0.02e0.09)
0.13 (0.06e0.29)

0.30 (0.06e1.08)

0.11 (0.08e0.30)
0.17 (0.01e3.07)

0.02 (<LODe0.39)
2.30 (0.07e6.57)

0.03 (0.02e0.05)

0.20
0.005
0.15
0.03
0.28
0.02
0.03

(0.06e1.13)
(0.001e0.007)
(0.06e0.57)
(0.01e0.23)
(0.10e0.75)
(0.01e0.03)
(0.009e0.08)

NW Alaskae
0.06
0.26
0.006
0.14
0.27

(0.009e0.19)
(0.03e0.59)
(0.001e0.02)
(0.07e0.62)
(0.01e1.06)

2.79 (0.19e9.20)

1.07 (0.12e4.00)

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Table 3
Comparison of literature values concentration level ranges of heavy metals in urban
background snow samples and measured values in Cerro Colorado (CC) and Nevados
de Chilln (NCH). All data in mg kg1.
Sampling site Cu

Zn

Cd

Pb

Cincinnati

5e35

0.2e0.35

0.5e10

Lulea
Sundsvall
Innsbruck
CC
NCH

2e10

Source

Glenn and Sansalone,

2002
5e70 25e410 e
4e45
Reinosdotter and
Viklander, 2005
1e10 5e70
e
8e17
Reinosdotter and
Viklander, 2005
10e40 50e300 0.25e11.54 0.2e33
Engelhard et al., 2007
5e387 10e114 0.13e2.20 2.4e74.9 This work
1e18 13e17 0.14e0.80 1.8e13.5 This work

range of previously published values in the urban reference areas of

Cincinnati and Sundsvall, but lower than reference values from
Lulea and Innsbruck. Zn levels in Nevados de Chilln samples gave
values within the lower end range of Cincinnati and Sundsvall
values. Concentration values for Cd at Cerro Colorado were lower
than those found by Engelhard et al. (2007) in background areas of
Innsbruck, but higher than the values reported at Cincinnati by
Glenn and Sansalone (2002). These latter values were similar to our
Cd results in the samples taken at Nevados de Chilln. Relatively
elevated values of Pb concentration were observed in Cerro
Colorado snow samples with respect to previously reported values
in Cincinnati and Sundsvall, but similar to variability ranges in Lulea
and Innsbruck. Nevados de Chilln Pb values are similar to those
found in urban reference areas of Sundsvall by Reinosdotter and
Viklander (2005). These results are in support of the previous
conclusion about the impact of Santiago de Chile urban emissions
on snow precipitation at Cerro Colorado, probably combined with
the effect of mining-smelting activities in the area.
3.2. Comparison between Cerro Colorado and Nevados de Chilln
A detailed study of anthropogenic elements concentration in the
snow samples was then conducted to evaluate the relative impact

55

of pollution sources around Santiago de Chile with respect to the

regional reference area at Nevados de Chilln. A detailed view of
Cerro Colorado vs Nevados de Chilln data sets is provided in Fig. 3,
showing the signicant differences observed for most elements
between the two sampling sites. Table 4 summarizes anthropogenic sources that can be assigned to elements assayed in atmospheric deposition according to published literature: trafc (Querol
et al., 2001), smelting (Alastuey et al., 2006), biomass and coal
burning (Andersen et al., 2007) and waste incineration (Harrison
et al., 1996). It also reects experimental mean values in the
assayed snow samples and calculated concentration ratios (mean
element concentration at CC/mean element concentration at NCH).
Higher mean concentrations of anthropogenic elements were
found in Cerro Colorado compared with the Nevados de Chilln
reference area, with concentration ratios ranging from 2.2 (Cd) to
108.1 (V). Average concentration ratios were calculated for groups
of elements linked to specic sources, with highest average ratio
found for trafc sources (30.4), followed by biomass and coal
burning (17.0), smelting sources (16.8), and waste incineration
(6.3). These preliminary results conrm the dominant impact of
urban trafc emission sources on the composition of the snow
collected at Cerro Colorado, with a signicant contribution of
smelting and burning activities.
3.3. Variability of the elements in the snowpack
2008 and 2009 sampling campaigns at Cerro Colorado included
collection of surface and deep samples, as described in the methods
section. The snow samples were taken one month after the last
snowing event, to inspect the degree of anthropogenic elements
enrichment due to dry deposition of atmospheric particulates on
the snow. The results are shown in Fig. 4, depicting the ratio
between element concentrations in surface and deep snow. Cr was
under the detection limit in deep samples, so the results for this
element were excluded. These preliminary results shown a high
variability within the snowpack, with signicant enrichment for all
the elements assayed in surface samples. A more detailed study

Fig. 3. Box and whisker plots showing the distribution of selected anthropogenic elements concentrations in the snow from sampling areas at Cerro Colorado (CC) and Nevados de
Chilln (NCH).

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F. Cereceda-Balic et al. / Atmospheric Environment 47 (2012) 51e57

Table 4
Enrichment of anthropogenic tracer elements concentrations measured in the
snow samples collected during the sampling campaigns at Cerro Colorado (CC) vs
reference values at Nevados de Chilln (NCH). Sources traced: trafc (1); smelting
(2); biomass and coal burning (3); waste incineration (4).
Element

Sources traced

Cerro Colorado
mean (mg kg1)

Nevados de Chilln
mean (mg kg1)

Conc. ratio
CC/NCH

As
Pb
Cd
Ni
V
Cr
Mn
Co
Ba
Cu
Zn
Mo
Sb

2,
1,
1,
2
1,
1,
1,
2
1
1,
1,
1,
1,

1.50
28.66
0.74
1.92
1.36
1.36
46.06
1.35
27.36
105.51
51.07
0.71
0.11

0.04
8.21
0.33
0.26
0.01
<LOD
0.52
0.18
0.68
6.24
15.05
0.09
0.04

37.5
3.5
2.2
7.3
108.1

3
2, 4
2
2, 3
2
2

2,
2,
2,
2,

3, 4
3, 4
3
3, 4

88.4
7.6
40.0
16.9
3.4
7.8
3.1

including sampling of individual snowing events would be necessary to fully characterize elements distribution in the snow during
the winter season.

3.4. Temporal variability of the data at Cerro Colorado

Comparison of the concentration of anthropogenic elements in
the surface snow taken at Cerro Colorado during the 2003, 2008
and 2009 sampling campaigns (Table 5) was conducted to inspect
possible correlations of seasonal snow composition with changes in
the urban atmosphere of Santiago de Chile. These are measured by
a network of eight monitoring stations (Macam network) distributed around the city and operated by the Ministry of Health, and
translated to a set of air pollution indexes (Gramsch et al., 2006). Air
pollution indexes related to particulate matter levels showed
a steady decrease from 1997 to 2005, as a result of pollution control
strategies developed after the Chilean Environmental Base Law
(Conama, 1994) and a specic plan for decontamination of Santiago
(Conama, 1997). The decreasing trend of particulate matter indexes
was however reversed in the period 2005e2008 after the natural
gas supply shortage from Argentina caused signicant changes in
energy consumption modes, with increased use of diesel, coal and
biomass burning in Chile (Comisin Nacional de Energa, 2011).
Improved efforts directed to pollution control in Santiago de Chile
metropolitan area are currently in progress (PPDA, 2010). Our
results for elemental concentrations in the snow present
a minimum in the year 2003 for As, Pb, Mo and Sb, while in 2008

Table 5
Temporal evolution of the concentration of anthropogenic elements in the surface
snow taken at Cerro Colorado during the 2003, 2008 and 2009 sampling campaigns.
All concentrations in mg kg1.
Element 2003
As
Pb
Cd
Ni
V
Cr
Mn
Co
Ba
Cu
Zn
Mo
Sb

0.76
3.99
0.15
2.99
1.02
2.97
61.46
1.08
38.87
97.89
75.33
0.27
0.02

2008
(0.33e1.26)
2.01 (0.55e3.33)
(2.63e5.98)
61.47 (38.90e74.86)
(0.13e0.19)
1.37 (0.84e2.18)
(1.84e4.92)
2.24 (0.49e3.75)
(0.79e1.47)
2.75 (0.47e4.94)
(1.82e4.69)
1.12 (0.25e1.76)
(17.15e123.35) 74.66 (15.49e133.82)
(0.38e1.56)
2.52 (0.26e5.34)
(12.82e70.42)
37.28 (4.61e77.84)
(42.66e162.43) 189.46 (26.05e386.68)
(31.83e114.46) 49.63 (18.55e72.37)
(0.21e0.36)
1.27 (0.73e1.68)
(0.01e0.04)
0.18 (0.15e0.20)

2009
1.74 (1.65e1.87)
20.54 (13.02e31.26)
0.70 (0.67e0.72)
0.52 (0.37e0.81)
0.31 (0.13e0.46)
0.01
11.60 (5.52e16.96)
0.47 (0.11e0.66)
5.93 (1.97e9.80)
29.19 (12.21e38.44)
28.26 (18.76e37.07)
0.61 (0.27e0.91)
0.13 (0.13e0.15)

the concentrations of As, Pb, Cd, V, Mn, Co, Cu, Mo and Sb were
maximum, probably reecting the impact of signicant changes in
the energy sources distribution at Santiago de Chile during the
studied period. Ni, Cr, Ba (no biomass or coal burning tracers) and
Zn showed a different trend with decreasing values from 2003 to
2009. These preliminary results support the potential use of snow
analysis at Cerro Colorado for indicating changes in the urban
atmosphere of Santiago.
4. Conclusions
This work has demonstrated that anthropogenic trace element
levels in snow precipitation at sampling locations in Cerro Colorado,
Central Andes, about 40 km NE from the metropolitan area are
affected by urban atmospheric emissions from Santiago de Chile. A
simple methodological approach consisting in surface snow
sampling and analysis by a standardized ICP-MS method (including
proper precautions to avoid sample contamination), provide information about spatial distribution and temporal evolution of the
atmospheric precipitation at the selected sampling locations.
Signicant enrichments for a variety of trace element markers,
related to trafc, smelting and biomass burning were found in
Cerro Colorado, by comparison with relatively undisturbed locations at Nevados de Chilln, 500 km S. Temporal evolution of trace
element levels at Cerro Colorado, between 2003 and 2009, were
correlated with changes in Santiago de Chile urban atmospheric
emissions in the same period.
Our preliminary results have shown that snow precipitation in
the Central Andes could be a suitable matrix for receptor model
studies aimed at identifying and quantifying pollution sources at
Santiago de Chile, as a simple and affordable methodology to
complement the information of urban atmospheric surveillance
networks.
Acknowledgements
This work was supported by Agencia Espaola de Cooperacin
Internacional al Desarrollo (AECID), project D/031258/10. Additional support from projects CONICYT: FONDEF D05-I-10054,
FONDECYT 1070500; DGIP-USM N 13.09.57 and Junta de Extremadura (Spain) is also acknowledged.
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Fig. 4. Elemental concentration ratios (surface vs deep) in snow at Cerro Colorado

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